Oximinophosphonodithioates

ABSTRACT

Compounds having the formula   IN WHICH R is alkyl; R1 is hydrogen; nitro, or halogen, R2 is alkyl; and R3 is (1) hydrogen, (2) lower alkylthio, (3) cyano, (4) alkyl, and (5) ethynyl and their use as insecticides and acaricides.

United States Patent [1 1 Gutman [54] OXIMINOPHOSPHONODITHIQATES [75]Inventor: Arnold D. Gutman, Berkeley, Calif.

[73] Assignee: Stauffer Chemical Company, New

York,N.Y.

[22] Filed: April 6, 1970 [21] Appl. No.: 26,151

[52] US. Cl. ..260/940, 260/944, 260/972,

260/973, 424/210, 424/211 [51] Int. Cl. ..C07f 9/06, AOln 9/36 [58]Field of Search ..260/940, 944

[ 51 Jan. 9, 1973 Feb. 26, 1969 p. 147.

Primary Examiner-Lewis Gotts Assistant Examiner-Anton H. SuttoAttorney-Daniel C. Block, Edwin H. Baker and Albert J. Adamcik [57] vABSTRACT Compounds having the formula R R S S CH2-R in which R is alkyl;R is hydrogen; nitro, or halogen, R is alkyl; and R is (1) hydrogen, (2)lower alkylthio, (3) cyano, (4) alkyl, and (5) ethynyl and their use asinsecticides and acaricides.

5 Claims, No Drawings OXIMINOPHOSPHONODITHIOATES This invention relatesto certain novel chemical compounds and their use as insecticides andacaricides. More particularly, the chemical compounds are certainoximinophosphonodithioates.

The compounds of this invention are those having the formula loweralkylthio having one to two carbon atoms; (3)' cyano; (4) alkyl havingone to five carbon atoms, (5) ethynyl.

The compounds of the present invention can be prepared according to thefollowing reactions in which R, R, and R are as defined.

In the event that the desired compound cannot be prepared because ofdifficulty of preparing or obtaining the compound l-lSCH R of reactionl(b), then the following reaction can be utilized to obtain thecompounds of this invention.

in which 11k, R and R are as defined and is chlorine, bromine, oriodine.

Preferably, reaction l(a) is carried out by reacting preferably equalmole amounts of the two reactants. If an excess of either reactant isused, the reaction still proceeds but yields are reduced. The reactantscan be combined in any desired manner, but preferably, the reaction isrun in a solvent such as THF by first preparing the salt of the oximereactant with an acid acceptor such as potassium t-butoxide at roomtemperature and then preferably, slowly adding the dichloride reactantthereto, preferably in solution with a solvent, for example, THF, at atemperature below about 15C. for control. However, the oxime reactantcan be used in place of the salt, preferably in the presence of the acidacceptor. The resulting product is recovered and purified by standardprocedure. For example, the resulting product can be recovered from thereaction mixture and purified from the reaction mixture by adding themixture to a non-polar solvent such as benzene. The benzene mixture isthen washed with water, dilute NaOH solution and then again by water.The benzene is evaporated after the water has been removed, for ex--ample, by treatment with anhydrous MgSO. to yield the purified product.

Reaction l(b) is carried out by reacting preferably equal mole amountsof the two reactants. If an excess of either reactant is used, thereaction still proceeds but yields are reduced. The reactants can becombined in any manner but preferably the phosphorus containing reactantis lowly added to the reactant containing the SH group in a solvent suchas THF, preferably with stirring. More preferably, an alkali metal saltof this reactant is used to reduce the chance of a violent reaction. Thetemperature of the reaction is not critical, however, better yields areobtained by heating the reactants at reflux for a time sufficient toallow completion of the reaction. The resulting product can be recoveredfrom the reaction mixture by adding the mixture to a non-polar solventsuch as benzene. The benzene mixture is then washed with water, diluteNaOH solution and then again by water. The benzene is evaporated afterthe water has been removed, for example, by

. treatment with anhydrous MgSO. to yield the purified product. Theprocess represented by reaction ll(a) is carried out by merely reactingthe two reactants. Preferably, about 2 moles of the oxime reactant permole thionophosphine sulfide reactant should be used. If an excess ofeither reactant is used, the reaction still proceeds but yields arelowered. The reactants can be combined in any desired manner. Thereaction readily proceeds at room temperature and preferably is rununder anhydrous conditions in a common solvent for the reactants such asbenzene. The dithiophosphonic acid product can be recovered from itssolvents in pure form, but it is preferred to not do so. If prolongedstorage of the compound is desired, it is preferably to prepare eitherthe alkali, alkaline or heavy metal salt of the acid.

Reaction ll(b) utilizes as a reactant the product of reaction ll(a)preferably as a solution in the solvent utilized for reaction ll(a). Inthis process, the reaction thio-ethyl)-phosphono dithioate.

reactant to a solution of the dithiophosphonic acid reactant, preferablythe acid is not recovered from the solvent in which it is prepared.Preferably, the reaction is carried out at below room temperature aboutl-20 C. for control and in the presence of a base, such astriethylamine, to take up the liberated acid halide reaction product.The reaction product is recovered by conventional means such asdescribed for. reaction [(12).

Preparation of the compounds of this invention is illustrated in thefollowing examples:

EXAMPLE I O-( 4-chloro-acetophenoneoximino),ethyl-S-(methyl on, sultrasonic H;

12.4 gms. (0.05 moles) of ethylthionophosphine sulfide, 17 gms. (0 .l02moles) of 4- chloroacetophenoneoxime and 200 ml. of dioxane are combinedin a l Lbeaker and stirred magnetically at room temperature until -a'solution is obtained. The

solution is stirred and cooled tov C. in an ice bath.

ll.l gms. (0.1 moles) of chloromethyl ethylsulfide is added, followed by15.1 gms. (0.15 moles) of triethylamine added over a period of 10minutes. The resulting mixture is stirred at room temperature for 1hour, then poured into 500 ml. of benzene and consecutively, washed with200 ml. of water, 100 ml. of saturated sodium bicarbonate solution, and2 100 ml. portions of water. The benzene phase is dried with anhydrousMgSO, and evaporated to yield 28 gms. (72.5 percent of theory) of thedesired product. N

The following is a Table of certain selected compounds that arepreparable according to the procedure described hereto. Compound numbersare assigned to each compound and are used throughout the remainder ofthe application.

9 CH, -4-Cl C li CN 1.5868 10 CH, 4-Cl QB, C=CH 1.6043 1 1 CH, 4-Cl CJl,-SCl-l 1.6217 12" CH, 4-Cl CJ-l -SC,H l .6203 F Prepared in Example IThe following tests illustrate the insecticidal and acaricidal activityof the compounds of this invention.

INSECTICIDAL EVALUATION TESTS The following'insect species were used inevaluation tests for insecticidal activity:

I l. Housefly (HF) Musca domestica' (Linn.)

2. German Roach (GR) Blatella germanica (Linn.)

3. Saltmarsch Caterpillar (SMC) Estigmene acrea (Drury) 4. Lygus Bug(LB) Lygus hesperus (Knight) 5. Bean Aphid (BA) Aphisfabae (Scop.)

The l-lousefly (HF) was used in evaluation tests of selected compoundsas insecticides by the following procedure. A stock solution containingug/ml of the toxicant in an appropriate solvent was prepared. Aliquotsof this solution were combined with 1 milliliter of an acetone-peanutoil solution in an aluminum dish and allowed to dry. The aliquots werethere to achieve desired toxicant concentration ranging from 100 pg perdish to that at which 50 percent mortality was attained. The dishes wereplaced in a circular cardboard cage, closed on the bottom withcellophane and covered on top with cloth netting. Twenty-five femalehouse-flies, 3 to 5 days old, were introduced into the cage and thepercent mortality was recorded after 48 hours. The LD-50 values areexpressed in terms of pg per 25 female flies. The resulsts of theseinsecticidal evaluation tests are given in Table ll under HF.

In the German Cockroach (GR) tests, 10 l-month old nymphs were placed inseparate circular cardboard cages sealed on one end with cellophane andcovered by a cloth netting ong the other. Aliquots of the toxicants,dissolved in an appropriate solvent, were diluted in water containing0.002 percent of a wetting agent, Sponto 221, (a polyoxyether ofalkylated phenols blended with organic sulfonates). Test concentrationsranged from 0.1 percent downward to that at which 50 percent mortalitywas obtained. Each of the aqueous suspensions of the candidate compoundswas sprayed .onto the insects through the cloth netting by means of ahand-spray gun. Percent mortality in each case was recorded after72'hours, and the LD-50 values, expressed as percent of toxicantin theaqueous spray, were recorded. These values are reported under the columnGR in Table 11.

For testing the Salt-marsh Caterpillar, test solutions were prepared inan identical manner and at concentrations the same as for the GermanCockroach, above. Sections of bitter dock, Rumex obtuszfalus, leaves, 11.5 inches in length were immersed in the test solutions for-l0 to 15seconds and placed on a wire screen to dry.

The dried leaf was placed on a moistened piece of filterwhich 50 percentmortality was obtained. After 24 and 72 hours, counts were made todetermine living and dead insects. The LD-SO (percent) values werecalculated. These values are reported under the column LB in Table n.

These results are given in Table 11 under the Column BA."

ACARICIDAL EVALUATION TEST The two-spotted mite (28M), Tetranychusurticae (Koch), was employed in tests for miticides. Young pinto beanplants or lima bean plants (Phaseolus sp.) in the primary leaf stagewere used as the host plants. The young pinto bean plants were infestedwith about 100 mites of various ages. Dispersions of candidatemateripinto bean plants were placed in bottles containing 200 ml. of thetest solution and held in place with cotton plugs. Only the roots wereimmersed. The test solutions were prepared by dissolving the compoundsto be tested in a suitable solvent, usually acetone, and then dilutingwith distilled water. The final acetone concentration never exceed about1 percent. The toxicants were initially tested at a concentration of 10parts per million (p.p.rn.). Immediately after the host plant was placedin the test solution it was infested with the test species. Mortalitieswere determined after 7 days.

Young nasturtium plants were used as the host plants for the Bean Aphid.The host plants were transplanted into one pound 6f soil tha t h ad beentreated with the candidate compound. Immediately after planting in thetreated soil the plants were infested with aphids. Con- :centrations oftoxicant in the soil ranged from 10 p.p.rn. per pound of soil downwarduntil an LD-SO value was obtained. Mortality was recorded after 72hours. A

The percentage of kill of each test species was determined by comparisonwith control plants placed in distilled water or untreated soil. TheLD-50 values were calculated. These systemic test results are reportedin Table II under the columns BA-Sys and f2SM-Sys.

Percent Percent Compound HF, m BA-SYS, SYS, Number pg. GR LB SMC BAp.p.rn. PE EGGS p.p.rn. 20 .1 .03 .1 008 .01 10 als were prepared bydissolving 0.1 gram in 10 ml. of a suitable solvent, usually acetone.Aliquots of the toxicant solutions were suspended in water containing0.002% v/v Sponto 221, polyoxyethylene ether sorbitan monolaurate, anemulsifying agent, the amount of water being sufficient to giveconcentrations of active ingredient ranging from 0.05 percent to that atwhich percent mortality was obtained. The test suspensions were thensprayed on the infested plants to the point of run off. After sevendays, mortalities of postembroyonic and ovicidal forms were determined.The percentage of kill was determined by comparison with control plantwhich had not beensprayed with the candidate compounds. The LD-SO valueswere calculated using well-known procedures. These values are reportedunder the columns ZSM-PE and ZSM-Eggs in Table ll.

SYSTEMIC EVALUATION TEST This test evaluates the root absorption andupward translocation of the candidate systemic compound. The two-spottedmite (28M) Tetranychus urticae, (Koch) and the Bean Aphid (BA) Aphisfabae (Scop.) were employed in the test for systemic activity.

Young pinto bean plants in the primary leaf stage were used as hostplants for the two-spotted mite. The

As those in the art are well aware, various techniques are vailable forincorporating the active component or toxicant in suitable pesticidalcompositions. Thus, the

pesticidal compositions can be conveniently prepared in the form ofliquid or solids, the latter preferably as l homogeneous free-flowingdusts commonly formulated shell, sheat, soya bean, cottonseed and soforth.

Liquid compositions are also useful and normally comprise a dispersionof the toxicant in a liquid media, although it may be convenient todissolve the toxicant directly in a solvent such as kerosene, fuel oil,xylene, alkylated naphthalenes or the like and use such organicsolutions directly. However, the more common procedure is to employdispersions of the toxicant in an aqueous media and such compositionsmay be produced by forming a concentrated solution of the toxicant in asuitable organic solvent followed by dispersion in water, usually withthe aid of surface active agents. The latter, which may be the anionic,cationic, or nonionic types, are exemplified by sodium stearate,potassium oleate and other alkaline metal soaps and detergents such assodium lauryl sulfate,-

sodium naphthalene sulfonate, sodium alkyl s s tini iu in which R isalkyl having one to four carbon atoms; R is hydrogen nitro or halogen; Ris alkyl having one to four carbon atoms, and R is (l) ethynyl (2) loweralkylthio having one to two carbon atoms, or (3) cyano.

2. The compound of claim 1 in which R is methyl, R is hydrogen, R isalkyl having one to two carbon atoms and R is lower alkylthio having oneto two carbon atoms.

3. The compound of claim 1 in which R is methyl, R is 4-chloro, R isalkyl having one to two carbon atoms and R is lower alkylthio having oneto two carbon atoms. 7

4. The compound of claim 1 in which R is methyl, R is 4-chloro, R isalkyl having one to two carbon atoms and R is cyano.

5. The compound of claim 1 in which R is methyl, R is 4-chloro, R isalkyl having one to two carbon atoms and R is ethynyl.

2. The compound of claim 1 in which R is methyl, R1 is hydrogen, R2 isalkyl having one to two carbon atoms and R3 is lower alkylthio havingone to two carbon atoms.
 3. The compound of claim 1 in which R ismethyl, R1 is 4-chloro, R2 is alkyl having one to two carbon atoms andR3 is lower alkylthio having one to two carbon atoms.
 4. The compound ofclaim 1 in which R is methyl, R1 is 4-chloro, R2 is alkyl having one totwo carbon atoms and R3 is cyano.
 5. The compound of claim 1 in which Ris methyl, R1 is 4-chloro, R2 is alkyl having one to two carbon atomsand R3 is ethynyl.